Cationic azo dyes

ABSTRACT

WHEREIN R1 and R2 are each lower alkyl which may be substituted by a hydroxy radical, R3 is a benzyl group, a cyclohexyl group, or a lower alkyl group which may be substituted by a hydroxy radical, R4 is a normal or branched-chain alkylene radical having two to four carbon atoms, X1 and X2 are each hydrogen, chlorine, bromine, lower alkyl or lower alkoxy, Z is the radical of a coupling component, X is chlorine or bromine, and wherein R1, R2 and R3, or R2 and R3 together with the contiguous nitrogen atom may represent a monocyclic group.   Cationic azo dyes which are particularly suitable for dyeing synthetic fibers as well as natural fibers having the formula:

United States Patent Doss [4 1 Sept. 26, 1972 [54] CATIONIC AZO DYES [57] ABSTRACT I7 Inventor! posal oudgr yillmNX- Cationic azo dyes which are particularly suitable for Assignee: GAF Corporation New York NY. dyeing synthetic fibers as well as natural fibers having the formula. [22] Filed: Oct. 20, 1969 X Y 1 [21] Appl. No.: 867,912

' R N=N--Z [52] U.S. Cl. ..260/156, 260/ 152, 260/154, R R,-o0o 1 260/155, 260/162, 260/163, 260/187, 260/193, 260/196, 260/197, 260/199, m .7 .t 2 1 1 260/207, 260/207.l, 260/295 R, 260/471 R wherein R and R are each lower alkyl which may be [51] Int. Cl. ..C09b 29/08 substituted by a hydroxy radical, R is a benzyl group, [5 8] Field of Search ..260/156, 207.1, 152 a cyclohexyl group, or a lower alkyl group which may be substituted by a hydroxy radical, R is a normal or [56] References Cited branched-chain alkylene radical having two to four carbon atoms, X and X are each hydrogen, chlorine, UNITED STATES PATENTS bromine, lower alkyl or lower alkoxy, Z is the radical 2,128,255 8/1938 Krzikalla et al ..260/187 of a coupling COmPOHeHt X is chlmine or bromine 2,821,526 l/l958 Boyd ..260/205 and wherein R2 and R3, or R2 and R8 together with Primary Examiner-Lewis Gotts Assistant Examiner-Donald M. Papuga Attorney-Samson B. Leavitt and Walter C. Kehm the contiguous nitrogen atom may represent a monocyclic group.

l 1 Claims, No Drawings 1 CATIONIC AZO was This invention relates'to azo dyes, and more particularly, this invention relates to cationic azo dyes.

. Azo dyes have been used to dye natural fibers, such as wool and silk. It has been found in the past that certain azo dyes are particularly useful for dyeing synthetic fibers, such as acrylics. Furthermore, it has been found that cationic azo dyes are particularly useful for dyeing acrylic fibers and wherein R and R are each lower alkyl.

vA new class of cationic azo dyes now has been found which are particularly useful for dyeing acrylic fibers and cationic dyeable nylon. These dyes are also useful to dye wool and silk, as well as acrylic fibers in a mixture with other fibers, such as wool or cellulo'sic materials. These dyes are represented by the general formula:

N=N-z' R1 R -Rr-OOC 2 wherein'R is a lower alkyl group, R is a lower alkyl group which may be substituted by a hydroxy radical, R is a benzyl group, a cyclohexyl group, or a lower alkyl group which may be substituted by a hydroxy radical, R is a normal or branched-chain alkylene radical having two to four carbon atoms, X and X are each hydrogen, chlorine, bromine, lower alkyl or lower alkoxy, Z is the radical of a coupling component devoid of solubilizing sulfonic and carboxylic acid groups, Y is chlorine or bromine, and wherein R R and R or R or R together with the contiguous nitrogen atom may represent a monocyclic heterocyclic group. The dyes of the aforementioned formula have good light and wash fastness and good build-up properties. Additionally, they are capable of fast dyeing and have excellent sublimation properties.

Accordingly, it is a primary object of the present invention to provide a new class of dyes for dyeing both natural and synthetic fibers.

Y It is a further object of the present invention to provide a new class of azo dyes which are useful for dyeing such synthetic fibers as acrylic fibers.

It is yet another object of the present invention to provide a new class of cationic azo dyes which are particularly useful for dyeing acrylic fiber and cationic dyeable nylon, as well as wool and silk and mixtures thereof.

The dyes of the present invention are prepared in a conventional manner by esterifying a nitrobenzoyl chloride with a halo alcohol, and then treating the esterified product with an amine in order to form the quaternary ammonium derivative of the ester. The nitro group is then reduced to an amine, which is diazotized and coupled in a known manner with a coupler. As an alternative, the non-quaternized dyestuff can be produced and quaternization may be the last step of the reaction.

The following nitrobenzoyl chloride derivatives may be employed:

m-nitrobenzoyl chloride p-nitrobenzoyl chloride 4-methyl-m-nitrobenzoyl chloride 4-methoxy-m-nitrobenzoyl chloride 2-chloro-m-nitrobenzoyl chloride 2-chloro-p-nitrobenzoyl chloride 3-chloro'p-nitrobenzoyl chloride 3-bromo-p-nitrobenzoyl chloride 2-chloro-p-nitrobenzoyl chloride 3,5-dichloro-p-nitrobenzoyl chloride 2,5-dimethyl-p-nitrobenzoyl chloride The haloalcohols which are employed in the esterification are exemplified as follows:

2-chloroethanol 3-chloro-l-propanol l-chloro-Z-propanol 4-chloro-l-butanol l-chloro-2-butanol 4-chloro-2-butanol chloro-tert. butanol and the corresponding bromo derivatives.

The following exemplify the amines which may be used in the quaternization:

trimethylamine triethylarnine tripropylamine tributylarnine dimethylethylamine methyldiethylamine dimethylcyclohexylamine diethylcyclohexylamine dimethylbenzylamine diethylbenzylamine dimethylethanolamine diethylethanolamine triethanolamine pyridine morpholine, then treated with CH (Cl-19 and the like l-methylpiperidine The coupling components which are suitable for use in this invention include all types of coupling components which are normally used in the production of azo dyes with the exception of those which contain solubilizing sulfonic acid and carboxylic acid-groups. They include those compounds which are capable of coupling because of amine groups, hydroxy groups or enolizable ketone groups.

Those which couple due to a p-directing amine substituent and which are of particular interest are exemplified by the following:

methylaniline dimethylaniline diethylaniline ethylbenzylaniline chloroethylethylaniline bromoethylethylaniline cyanoethylethylaniline di(hydroxyethyl)aniline acetoxyethylethylaniline carbethoxyethylethylaniline m-toluidine diethyl-m-toluidine cyanoethylethyl-rn-toluidine chloroethylethyl-m-toluidine hydroxyethylethyl-m-toluidine 2,5-dimethoxyaniline S-methyl-o-anisidine 3-Di( hydroxyethyl)aminoacetanilide 3-Diethylaminoacetanilide S-Diethylaminopropionanilide B-Diethylaminobutyranilide 3 4 3-Diethylamino-4-methoxyacetanilide 010 H O 3-Dimethylamino-4-ethoxyacetanilide 3-Cyanoeth leth lamino-4-methox acetanilide N.E h 1-3. 2- 1 245 g. of this product was combmegi with 350 ml. However, it is not intended to limit the coupling 5 pyndineiand heated overnight at It was hell components to compounds of the above type, as all cooled to C., filtered, washed with petroleum ether other azo coupling components which are free from and dried-The Product had the formula: sulfonic acid and carboxylic acid groups may be used,

p-cresol w m.p. l95.0-l95.8C., 232g.

4-phenylphenol l5 l -naphthylamine z h h l i I 121 g. of 60 mesh finely powdered iron, 250 ml. of N. h l.l. h h la i water and 5 ml. of formic acid were heated together at ml ene-2,4-di i 95 C., for I hour. It was cooled to about 80 C., and l-methyl-S-pyrazolone over a period of l to 2 hours. 100 g. of the product of l,3-dimethyl-5-pyrazolone I Example 1A was added. It was held at 80 C., fOlZ l-phenyl-3-methyl-5-pyrazolone hours, then cooled to 60 C. 7 g. of soda ash was then l-(3 nitropheriyl)-3-methyl-5-pyrazolone added to Brilliant Yellow alkalinity. It was filtered and l-(2,5-dichlorophenyl)-3-m hy -Py the filter cake washed with a little water. The filtrate 2-s y y and wash water were combined and acidified with 'P hydrochloric acid. An average yield was about 76per- F 9 cent theory, based on the initial 4-nitrobenzoyl 3-hydroxydibenzofurane N-methyl-Z,4-dihydroxyethylquinoline barbituric acid 3-hydroxy-2-naphthanilide 3-hydroxy-2-naphth-o-anisidide chloride. The product had the formula:

3-hydroxy-2'-methoxy-5 '-methyl-2-naphthanilide 3-hydroxy-N-( l-naphthyl )-2-naphthamide 3 ,-nitro-3-hydroxy- 2-naphthanilide acetoacet-o-anisidide 4'-chloro-2',5 Gdimethoxyacetoacetanilide EXAMPLE 2 3-nitro-3-hydroxy-2-naphthamhde 40 4 (5-chloro-2-hydroxyphenylazo)resorcino] Of the SOlUtlOl'l Of Example mole 7-hydroxy-4-(2-nitrophenylazo)- l -naphthylamine diazo) and 24 ml. of hydrochloric acid was iced to 0 C. 4-(2,5-dimethoxyphenylazo)phenol 4 18 ml. of sodium nitrite solution (31.5% NaNO was 4-(2,5-dimethoxyphenylazo)-N-ethyl-lstirredin slowly at 05 C. The excess nitrite was naphthylamine a g l y removed by treatment with sulfamic acid. 4 jl, y v y a 1.7 g. of dimethoxyaniline, 100 ml. of water and 12 Additionally, it is possible in the case where the ml. of hydrochloric acid were heated to solution, then pler has a free amine to treat the dyestufi with a comi f0 l C- a Poured n the diaZO. I a pound which is capable of forming a bis compound, Stirred 2 h treated Wi h 20 g- O dium acetate such as fumaryl-chlon'de or phosgene. In this latter and 20 g. of soda ash, filtered and dried, 60 g. of 9259 3 liie' l$tdlfi$itf PF9!q; Pmductbeing mined which had lefmulm l OCH:

The invention will be further described by reference The product dyes acrylic fibers in reddish orange t sf lw fis reali ies;s zearleatbstesfi 60 shades- 200 g. of 4-nitrobenzoyl chloride and 200 g. of 1 EX E3 chloroethanol were heated at l20-l2-5 C. for 8 hours. M The product was then poured into 800 ml. water at 5 -ss c., stirred for 5 minutes, let stand and their de- Examples 1 and 2 e repeated except that the canted. The water extraction was repeated twice. To nitfo-benloyl chloride a feplaeed y the same th h ge -add d 5 f di bi b at t H amount of 3-nitro-benzoyl chloride. This dyestuff is of 7-8. It was stirred to cool, filtered and vacuum dried. particular value for dyeing cationic dyeable nylon in Theprodu ci had the formula: orange shades.

3,694,426 5 6 EXAMPLES 4 52 meta position to the acyl group. In a manner similar to Examples 1 and 2, the followios ss f iweprsa r 5. The dye of claim 1, wherein the azo group is in the 6. The dye of claim 1, wherein X is hydrogen and X is selected from the group consisting of methyl, chloro,

Example Tert. amine Nitrobenzoyl chloride Coupler Color 4.. Pyridine 4-nitrobenzoyl chloride p-Cresol Yellow. 5 ....d0.... ..d l-nephthol. Yollowlsh red.

....do.. 2-nephthol Orange.

(10.. fi-(cllhydroxyethylnmlno) nootunllklo Yollowlsh rod. ..do.. 2-naphthylemine................................ Scarlet. .-do.. Dimethylenlline..... Omngo. do.. m-Toluldlne........ Yellow. ..do.. 1-nuphtliy1amlno Scnrlot. (10.. 3-dlothyleminonootunllldo- Ornngn. ..do.. N,N-dlethyl-m-toluldlnn. Yellow. do.-. fi-rnothyl-o-nnlsldlne Roddlsli yellow. ..do... 1-phonyl-3-methyl-lS-pyrn.zolnne (lroenlsh yellow. ..do l-methyl-B-p uzolone Do. ..do... N-cyenoethy -N-othyl-n1-toluldlne Rod. -do... N-othyl-N-(pyrldyl-Z-othyl)-m-toluldin0. Rod. .do... -benzyl-N-ethylenlllno Scarlet. .do... -Pheny1 henol Yellow. .do... -methy dloxyqulnoline.. Greenlsh yellow .do... Acetoacetanlsidlde Do. .do... 4-chlor0-2',5-dimothoxy-acetoacetanilide- Do.

. Toluene-2,4-diarn1ne Red. .do. 1-(2,5-diehlorophenyl)-3-methyl5-pyrazolono.-.- Greenish yellow. .-do. 1-(3-n1trophenyl)-3-mei;hyl-5-pyrazolone Do. .dol-(chlorophenyl)-3-methyl-5-pyrazolone... Do. do. Z-naphthol Orange- .do. I-nnphthol Yellowish orange. .do. l-mctliyl-5-pyrazolone Greenish yellow. .do. l-phcnyl-Zi-methyl-fi-pyrazolonc Do. .do. 5-methyl-o-anisidinc.... Yellowish orange.

do. N,N-diethyl-rn-toluidine.. Scarlet. .do. N,N-diethyl-m-acctanilide. Do. do. l-naphthylamlne Do. .do. p-Ores Yellow. do. m-Toluidine o. o. N,N-dlrnetl1ylamine..-. Orange. .do.

Z-naphthylaminc Do. .do. 2,5-dimethoxyaniline phenol Red. 41 ..do. 2,5dimethoxyanilino N-phenyl-l- Blue.

naphthylaminc. 42 'lriethanol-ammc l-phenyl-3-mothyl-5-pyrazolono. Yellow. 43... Dimethylcyclohexylamlnc.. ..do Grcenishyollow.

44-.. Dimethylbenzylaminc..... Do. 45-.. 'lricthylarninc ..do. 46-.. Pyridine 3-nitro-p-toluoyl chloride. 47... do... 24thloro-3-nltro-p-toluoyl ch .48... .....do... 2-bromo-3-nitro-p-toluoylchlorid 49-.. do. 3-mcthoxy-4-nitro benzoylchlm-idr 50... ..do... 3-cthoxy-4-nitro-benxoylchloride. 51 do.. 4-mcthoxy-3-nitro benzoylchlorldc 52 .do 4-nitrobonzoylcliloride What is claimed is: 1- Asetionic y v nafi s Q TSBPF...

bromo, methoxy and ethoxy radicals.

radicals.

7. The dye of claim 1, wherein X and X are chlorine r 8. The dye of claim 1, wherein X and X are methyl radicals. N=N Z Y 9. The dye of claim 1, wherein L X2 R r u wherein R and R5 are each lower alkyl or hydroxy-substituted lower alkyl, R, is benzyl, cyclohexyl, lower alkyl or hydroxy-substituted lower alkyl, R. is selected from the group consisting of normal and branched chain alkylene radicals having to to four carbon atoms, dimethylbenzylqmno methylammo P X and X are each hydrogen, chlorine, bromine, lower ?P dye:

alkyl or lower alkoxy, Z is the radical of a coupling component devoid of solubilizing sulfonic and carbox- 5 ylic acid groups and containingp tg ileirleectipngg W111 4. The dye of claim 1, wherein the azo group is in the 5 I substituen m a benzene or na N -CrH400CO-N=N NH; 01- chlorine or bromine and additionally w H or- .0 1 1. The cationic azo dye:

OOH: may represent pyrldyl, morphollnyl or pipericlinyl.

2. The dye of claim 1, wherein R is ethylene. v 3. The dye of claim 1, wherein X and X, are 5 \e hydrogen. N-CzH4OOC (ion,

.represents triethanolamino, dimethylcyclohexylamino,

ara' sition to the ac l ou p PO YET. P 

2. The dye of claim 1, wherein R4 is ethylene.
 3. The dye of claim 1, wherein X1 and X2 are hydrogen.
 4. The dye of claim 1, wherein the azo group is in the para position to the acyl group.
 5. The dye of claim 1, wherein the azo group is in the meta position to the acyl group.
 6. The dye of claim 1, wherein X1 is hydrogen and X2 is selected from the group consisting of methyl, chloro, bromo, methoxy and ethoxy radicals.
 7. The dye of claim 1, wherein X1 and X2 are chlorine radicals.
 8. The dye of claim 1, wherein X1 and X2 are methyl radicals.
 9. The dye of claim 1, wherein represents triethanolamino, dimethylcyclohexylamino, dimethylbenzylamino, triethylamino or pyridyl.
 10. The cationic azo dye:
 11. The cationic azo dye: 